Acryloylamino benzene monoazo dyestuffs



United States Patent 3,208,992 ACRYLOYLAMINO BENZENE MONOAZO DYESTUFFS Francis Bowman and Peter William Hickmott, Manchester, England, assignors to Imperial Chemical Industries Limited, London SW. 1, England, a corporation of Great Britain l\ o Drawing. Filed Dec. 21, 1962, Ser. No. 246,358 Claims priority, application Great Britain, Jan. 10, 1962, 977/ 62 1 Claim. (Cl. 260-162) This invention relates to new azo dyestuffs and more particularly it relates to new monoazo and disazo dyestuffs which are valuable for colouring textile materials, in particular woollen textile materials.

According to the invention there are provided the azo dyestuffs which are represented by the formula:

wherein Y Y and Y each independently represent a hydrogen or a chlorine atom, V represents a lower alkyl or a lower alkoxy radical, n represents 1 or 2, E represents the residue of .a coupling component, X represents a direct link or a -CH2CH2, CH=CH, CH2, -o-, CO -C OIf- SO2III- or --I?T- group R R, R wherein R represents a hydrogen atom or a lower alkyl radical, A represents a substituted or unsubstituted divalent hydrocarbon radical containing at least 5 carbon atoms, or when X represents -C Ol |I or SO2ITTA R R and R can together form with the nitrogen N a 6-membered heterocyclic ring, and Z represents a hydrogen atom or a H \C=O.CON

group, as hereinbefore defined, provided that the dyestuffs contain at least one sulphonic acid or carboxylic acid group attached to at least one of A and E.

A preferred class of the dyestuffs are the dyestuffs of the above formula wherein Y Y and Y each represent a hydrogen atom. It is further preferred that the dyestuffs contain only one sulphonic acid group which is attached to E.

The residue of the coupling component represented by B may be the residue of any of the known series of coupling components (that is to say a compound which will react with a diazonium compound to form an azo dyestuff), but E is preferably the residue of a coupling component of the phenol, naphthol, acylacetarylamide, arylamine, S-aminopyrazole or 5-pyrazole series. The coupling components of the acylacetarylamide series are preferably acetoacetanilides. The coupling components of the arylamine series may be primary, secondary or tertiary amines of the benzene series which couple in para position to a primary, secondary or tertiary amino group, and, above all, are primary amines of the naphthalene series which couple in para or preferably ortho position to a primary amino group. The coupling components of the S-aminopyrazole series are preferably l-aryl-S-aminopyrazoles in particular 1-p'henyl-5-aminopyrazoles. The

coupling components of the 5-pyrazolone series are preferably l-aryl-S-pyrazolones in particular l-phenyl-S-pyrazclones or 1-n:apht'hyl-S-pyrazolones. If desired the coupling components represented by B may contain substituents attached to aryl rings, in particular benzene or naphthalene rings, present in the said components; and as examples of such substituents there may be mentioned chlorine atoms, lower alkyl radicals, lower alkoxy radicals and nitro, cyano, lower alkylsulphone such as methylsulphone and ethyl sulphone, suphonamide and substituted sulphonamide groups such as N-lower alkyl sulphonamide, N:N-di(lower alkyl) sulphonamide, N-(hydroxy lower alkyl)sulphonamide and NzN-di-(hydroxy lower alkyl)sulphonamide groups for example sulphon-N- methylamide, sulphon-N-ethylamide, sulphon-N-propylamide, sulphon-N-(fi-hydroxyethyl)amide, sulphon-NzN- di(;3-hydroxyethyl)amide, sulphon-N:N dimethylamide, sulphon-N: N diethylamide and sulphon-N:N dipropylamide groups, acylamino groups such as acetylamino, propionylamino, benzoylamino, benzenesulphonylamino, p-toluenesulphonylamino, carbomethoxyamino, carboethoxyamino, carbopropoxyamino and groups, wherein Y Y and Y have the meanings stated, primary amino groups, N-lower alkylamino groups, phenylamino groups, sulphonic acid groups, carboxylic acid groups, and arylazo groups in particular substituted or unsubstituted phenylazo or naphthylazo groups.

It is however preferred that the residues of the coupling components represented by E contain at least one sulphonic acid group.

Throughout the specification the term lower alkyl or lower alkoxy is used to denote an alkyl or alkoxy radical respectively of low molecular weight, in particular an alkyl or alkoxy radical respectively containing from 1 to 4 carbon atoms; and as examples of such alkyl radicals there may be mentioned methyl, ethyl, propyl and butyl radicals, and as examples of such alkoxy radicals there may be mentioned methoxy and ethoxy radicals.

As examples of G-membered lheterocyclic rings which may be obtained by joining together A, R and the nitrogen atom N there may be mentioned piperidine, morpholine and piperazine rings.

As examples of the substituted or unsubstituted divalent hydrocarbon radicals represented by A there may be mentioned substituted or unsubstituted alkylene radicals containing at least 5 atoms, for example, pentamethylene, dimethyltrimethylene, hexamethylene, heptamethylene, ootamethylene, nonamethylene, 1: l :3 3-tetramethyl-tetr-amethylene, decamethylene and dodecamethylene radicals, divalent cyclic aliphatic radicals such as divalent cyclopentane, cyclohexane, and methylcyclopentane radicals, and substituted and unsubstituted divalent aromatic radicals, which are preferably monocyclic aromatic radicals, such as phenylene, tolylene, methoxyphenylene, chlorophenylene, b-romophenylene, sulphophenylene and carboxyphenylene radicals.

It is however preferred that A represents a substituted or unsubstituted phenylene radical.

According to a further feature of the invention there is provided a process for the manufacture of the azo dyestuffs, as hereinbefore defined, which comprises treating with an acylating agent, such as the acid halide, derived from an acid of the formula:

| HOOC.C

Formula I XA-Z Formula II wherein A, V, E, n and X have the meanings stated above,

and Z represents a hydrogen atom, a -NH or a -N.CO o=o Y3 group, wherein Y Y and Y have the meanings stated above, provided that the azo compounds of Formula II contain at least one sulphonic acid or carboxylic acid group.

This process of the invention may be conveniently brought about by adding the acylating agent to an aqueous solution of the azo compound, stirring the resulting mixture, preferably at a temperature between and 20 C., whilst maintaining the pH of the mixture between 6 and 7 by the addition of an acid-binding agent such as sodium carbonate or sodium acetate, adding sodium chloride and isolating the azo dyestuif which is precipitated.

As examples of acylating agents which may be used in this process of the invention there may be mentioned (at-chloroacryloyl chloride, p-chloroacryloyl chloride, acryloyll bromide, 13:5-dichloroacryloyd chloride, oHfiZB- trichloroacryloyl chloride and preferably acryloyl chloride.

The azo compounds of Formula II used in this process of the invention may themselves be obtained by diazotising an amine of the formula:

X-A-Z Formula 111 wherein A, V, n and X have the meanings stated above, Q represents a nitro group or an acetylamino group, and Z" represents a hydrogen atom, a nitro group, an acetylamino group or group, as hereinbefore defined, coupling the diazo compound so obtained with a coupling component of the formula EH, and finally converting the nitro or acetylamino group represented by Q or Z to an amino group by reduction or by hydrolysis, provided that the amine of Formula II and the coupling component are so chosen that the resulting azo compound contains at least one sulphonic acid or carboxylic acid group.

As examples of amines of Formula III which may be used to obtain the azo compounds of Formula II there may be mentioned -nitro-2-aminobenzenesulphon-N-ethylanilide,

5-nitro-2-aminobenzenesulphonanil-ide,

fi-acetylamino-2-aminobenzenesulphon-N-ethylanilide,

2-nitro-4-aminodiphenyl,

2-nitro-4 aminodiphenylamine,

5-nitro-2-aminodiphenyl,

2-amino-4:'4'-bis(acetylamino)diphenyl,

2-amino-4-acetylaminodiphenyl and N-acetyl-N-(2 amino45-nitrobenzenesulphonyl) piperazine.

As examples of coupling components of the formula: EH there may be mentioned phenols such as p-cresol, 4,-acetylaminophenol, resoroinol, 1-hydroxycarbazole-3 6- disulphonic acid and 2-hydroxycarbaZole-3:6:8-trisulphonic acid, naphthols such as l-naphthol, 1-naphthol-2-,

4-, or S-sulphonic acid, #1-naphthol-3:6- or -3:8-disulphonic acid, 1-naphthol-3:6:8-trisulphonic acid, Z-naphthol, 2-naphthol-6-, 7- or 8-sulphonic acid, Z-naphthol- 3:6- or 6:8-trisulphonic acid, l-amino-8-naphthol-2:4, -3:6 or -4:6-disulphonic acid and the N-lower alkyl, N- aryl and N-acyl derivatives thereof, 2-amino-8-naphthol- 6-sulphonic acid and the N-lower alkyl, N-aryl and N-acyl derivatives thereof, 2-amino-5-naphthol-7-sulphonic acid and the N-lower alkyl, N-aryl and N-acylderivatives thereof, 2-amino-8-naphthol-3:6-disulhponic acid, 2- amino-S-naphthol-l:7-disulphonic acid, 1-amino-8-naphthol-4-sulphonic acid, 1-amino-5-naphthol-7-sulphonic acid, N-(7-sulpho5-hydroxynaphth-2ryl)piperazine and N-(6 sulpho-8-hydroxynaphth-2-yl) piperazine; arylamines for example NzN-dimethylaniline, NzN-diethylm toluidine, m-toluidine, N:N-di(fl-hydroxyethyl)-mtoluidine, 1-naphthylamine-6- or 7-sulphonic acid, 2- methoxy-l-naphthylamine-6-sulphonic acid, 2 methylaminonaphthalene-7- sulphonic acid, Z-amino-S-n-aphthol- 6-sulphonic acid, 2naphthylamine-6-, 7- or 8-sulphonic acid, 2-naphthylene-3:7-, 428-, 5:7- or 6:8-disulphonic acid and the N-lower alkyl, N-aryl and N-acyl derivatives thereof, Z-naphthylamino-S- or 6-sulphonamide and 1- naphthylamine-Wsulphomethylamide; acylacetarylamides for example acetoacetanilide, acetoacetanilide-Iaor 4-sulphonic acid, acetoacet-3- or 4-aminoanilide, acetoacet-omor p-anisidide and acetoacet-oor p-chloroanilide; 5- amino-pyrazoles for example 1-phenyl-3-methyl-5-aminopyrazole; and 5-pyrazolones such as 1:3-dimethyl-5-pyrazolone, but more particularly l-aryl-S-pyrazolones such as 1-phenyl-3-methyl-5-pyrazolone, l-phenyl-3-carboxy-5-epyrazolone, 1-(2'-, 3- or 4'-sulphophenyl)-3-methyl-5-pyrazolone, 1-(2:4'- or 2':5'-disulphophenyl)-3-methyl-5- pyrazolone, 1-(3'- or 4'-aminophenyl)-3-methyl-5-pyrazolone, l-(3- or 4'-aminophenyl) 3-carboxy 5-pyrazolone, 1- 3 '-amino-4'-sulphophenyl) -3-methyl-5pyraz0lone, 1- (4'-amino-3'-sulphophenyl)-3-methyl 5 pyrazolone, 1- (5 hydroxy 7' sulpho-2-naphthyl)-3-methyl-5-pyrazolone and 1 (8' hydroxy-6'-sulpho-2-naphthyl) 3- methyl-S-pyrazolone.

According to a further feature of the invention there is provided an alternative process for the manufacture of the new azo dyestuffs, as hereinbefore defined, which comprises diazotising an amine of the formula:

V II- C= C O l Y NH1 XA Z Formula IV wherein A, V, X, Y Y Y n and Z have the meanings stated above, and coupling the diazo compound so obtained with a coupling component of the formula: EH wherein E has the meaning stated above, the amine and the coupling component being so chosen that the resulting azo dyestuif contains at least one sulphonic acid or carboxylic acid group.

This alternative process of the invention may be conveniently brought about by adding sodium nitrite to an aqueous solution or suspension of the amine in a dilute aqueous solution of hydrochloric acid, adding the resulting aqueous solution or suspension of the diazo compound to an aqueous solution of the coupling component, stirring the resulting mixture to effect formation of the azo dyestuff, and isolating by conventional methods, the azo dyestuff which is formed.

The amines of Formula IV used in this alternative process of the invention may themselves be obtained by treating a compound of the fomula:

wherein A, V, n, X and Z have the meanings stated above, with an acylating agent derived from an acid of Formula I, and subsequently reducing the nitro group to an amino group.

6 wherein X, V, T, n, r and p have the meanings stated, L represents a methyl or carboxy group, and the benzene ring I can optionally be substituted by chlorine atoms or by methyl or acryloylamino groups.

As specific examples of amines of Formula IV which can 5 The new azo dyestuffs of the invention are valuable for be used in the alternative process of the invention there colouring natural and artificial textile materials for ex- Inay be mentioned 2 amino-4:4'-bis(acryloylamino)diample textile materials comprising cotton, viscose rayon, phenyl, 2 amino-4:4-bis(acryloylamino)diphenylmethregenerated cellulose, wool, silk, polyamides and modified ane, 2 amino-4:4'-bis(acryloylamino)-5:5'-dimethyldipolyacrylonitrile fibres. For this purpose the dyestuffs phenyl, 2 amino 3 -bromo-4:4-bi-s(acryloylamino)dican :be applied to the textile materials by dyeing, padding phenyl, 4-amino-2:4'-bis(acryloylarnino)diphenylamine, or printing using in the latter case printing pastes con 2 amino 4:4-bis(acryloylamino)-5:5-dimethoxy-di taining the conventional thickening agents or oil-in-water phenyl, 2 amino-4:4-bis(acryloylamino)diphenylmethor water-in-oil emulsions, whereby the textile materials ane, 2-amino-4:4-bis(acryloylamino)stilbene, 2-amino-4- are coloured in bright shades possessing excellent fastacryloylaminostil-bene, 3 amino 5 acryloylamino- 1 ness to wet treatments such as washing. benzanilide, 3 amino 5 acryloylaminobenz-N-methy1- The new azo dyestuffs may be used as reactive dyeanilide, 3 amino 5 acryloylaminobenz-N-ethylanilide, stuffs for colouring cellulose textile materials. For this 2 amino 4 acryloylaminobenzanilide, 2-amino-4- purpose the dyestuffs are preferably applied to the celacryloylaminobenz N ethylanilide, 2-amino-4:4'-bislulose textile material in conjunction with a treatment (acryloylamino)benzanilide, 3 amino 5 acryloylwith an alkaline agent, for example sodium carbonate amino 2':4':6' trimethylbenzophenone, 2-amino-4- or bicarbonate, sodium metasilicate, trisodium phosphate acryloylaminobenzene sulphon-N-ethylanilide, Z-aminoor sodium hydroxide which may be applied to the cel- 4 acryloylaminobenzene sulphon-N-ethyl-3'-sulphoanlulose textile material before, during or after the applicailide and 2 amino-4-acryloylaminobenzene sulphon-N- tion of the dyestuff. Alternatively when the dyed textile methyl-3'-sulphoanilide. material is to be subsequently heated or steamed a sub- As examples of coupling components which can be stance, such as sodium trichloroacetate, which becomes used in the alternative process of the invention there may alkaline on heating or steaming, can be used. he mentioned any of the coupling components previously The new azo dyestuffs of the invention are particularly disclosed in the specification and, in addition, there may valuable for colouring nitrogen-containing textile ma- 'be used 2 acryloylamino-8-naphthol-6-sulphonic acid, terials, for example polyamide textile materials but, more 2 acryloylamino-8-naphthol-3:6-disulphonic acid, 2- particularly, woollen textile materials.

acryloylamino 5 n-aphthol-7-sulphonic acid, 2-acryloyl- The new azo dyestuffs of the invention can be applied amino-S-naphthol-l:7-disulphonic acid, 2-acryloylaminoto nitrogen-containing textile materials from a mildly 6 naphthylamine, acetoacet- 3 or 4-(acryloylamino)- alkaline, neutral or acid dyebath. The dyeing process anilide, 1-[3'- or 4'-(acryloylarnino)phenylJ-B-methyl or can be carried out at a constant or substantially concarboxy 5 pynazolone, l-[3'-sulpho-4(acryloylamino)- stant pH, that is to say the pH of the dyebath remains phenyl]-3-methyl-5-pyrazolone and l-[4'-sulpho-3'-(acrylconstant or substantially constant during the dyeing *oylamino)phenyl]-3-methyl-5-pyrazolone. process, or if desired the pH of the dyebath can be altered One preferred class of the azo dyestuffs of the invenat any stage of the dyeing process by the addition of tion are the monoazo dyestuffs which, in the form of the acids or acid salts or alkalis or alkaline salts. For exfree acids, are represented by the formula: ample dyeing may be started at a dyebath pH of about b- H2C=CI1LCOHN N=N l HgN- X soar (NH.CO.CII=C 2)p-l h-1 (CH)mwherein X has the meaning stated above, V represents 3.5 to 5.5 and raised during the dyeing process to about a lower alkyl or lower alkoxy group, T represents a 6.5 to 7.5 or higher if desired. The dyebath may also methyl, methoxy or sulphonic acid group, and n, m, p contain substances which are commonly used in the dyeand r each independently represent 1 or 2. ing of nitrogen-containing textile materials. As examples A second preferred class of the azo dyestuffs of the of such substances there may be mentioned ammonium invention are the monoazo dystulfs which, in the form of acetate, sodium sulphate, ethyl tartrate, nonionic dispersthe free acids, are represented by the formula: ing agents such as condensates of ethylene oxide with Example 1 A solution of 7.5 parts of the monosodium salt of 1-[4'-amino 2 (N-ethyl-N-phenylsulphamyl)phenylazo]-2-amino-8-naphthol-6-sulphonic acid in a mixture of 300 parts of water and 300 parts of acetone is cooled to 5' C., and 12 parts of acryloyl chloride are then added during 30 minutes, the pH of the mixture being maintained at 7 by the simultaneous gradual addition of an aqueous solution of sodium carbonate. The resulting mixture is stirred for 3 hours at a temperature between 5 and 10 C., 80 parts of sodium chloride are then added and the precipitated dyestutf is filtered off, washed with a 5% aqueous solution of sodium chloride and dried.

When applied to woollen textile materials from a neutral or slightly acid dyebath the dyestuif yields bluishred shades which possess excellent fastness to light and to wet treatments.

The monosodium salt of the azo compound used in the above example may itself be obtained by diazotising 5-nitro-2-aminobenzene sulphon-N-ethylanilide, coupling the resulting diazo compound with Z-amino-S-naphthol- 6-sulphonic acid in aqueous medium at a pH of 5, and finally treating the resulting compound with a hot aqueous solution of sodium sulphide to reduce the nitro group to an amino group.

Example 2 A solution of 1.5 parts of 2-amino-4:4'-bis(acryloylamino)-diphenyl in 50 parts of acetic acid is added to a pH of the mixture is adjusted to 5.0 and the mixture is then stirred for 18 hours at to C. The precipitated dyestufi' is then filtered off, washed with a aqueous solution of sodium chloride and dried.

When applied to woollen textile materials from a neutral or slightly acid dyebath the dyestuff yields bright yellowish-red shades which possess excellent fastness to light and to wet treatments.

I The 2-amino4:4'-bis(acryloylamino)-diphenyl used in the above example may be obtained as follows:

28 parts of acryloyl chlorideare added over 2 hours to a solution of 13 parts of Z-nitrobenzidine in a mixture of 400 parts of acetone and 100 parts of water at a temperature between 0 and 5 C., a 40% aqueous solution of sodium acetate. being simultaneously added to maintain the mixture neutral to Congo red. The resulting mixture is then stirred for 3 hours, and the precipitated 2-nitro-4:4'-bis(acryloylamino)-diphenyl is filtered off, washed with a 50% aqueous solution of acetone and finally dried.

A mixture of 7.95 parts of iron, 19 parts of ethanol, 4.75 parts of water and 0.2 .part of formic acid is stirred at the boil under a reflux condenser for 30 minutes. A suspension of 5 parts of 2-nitro-4:4'-bis(acryloylamino)- diphenyl in 2.0 parts of boiling ethanol is then added and the resulting mixture is stirred for hours at the boil under a reflux condenser. 0.22 part of sodium carbonate, 0.22 part of a 40% aqueous solution of sodium bisulphite and 100 parts of ethanol are then added, the mixture is heated to the boiling point and filtered. The

\ residue on the filter is washed with 100 parts of hot ethanol, and the combined filtrates are then evaporated to dryness in a vacuum when 2-amino-4:4'-bis(acryloy1- amino)-dipheny1 is obtained in the form of a white powder which melts at 225 C. with decompositionand subsequent resolidification.

The following table gives further examples of the new dyestuffs of the invention which are obtained when the sodium salts of the am compounds listed in the second column of the table are treated with the acid chlorides listed in the third column of the table by a method similar to that described in Example 1. The fourth column of the table gives the shades obtained when the resulting dyestuffs are applied to woollen textile materials.

Example Azo Compound Acid Chloride Shade 3 1-[4-amino-2-(N-ethyl-N-phenylsulphamyl)phenylazo1-2-naphthyl- Acryloyl chloride Scarlet.

amine-tS-sulphonic acid.

4 n a-chloroacryloyl ch1oride Do.

5 1-[4-amino-2-(N-phenylsulphamyl)phenylazo]-2-amin0-8-naph- Acryloyl chloride Bluish-red.

thol-G-sulphonic acid.

6 1-[4'-a.mino-2-(N-pipcridinosulphamyl)phenylazol-Z-amino-S- do Do.

naphthol-G-sulphonie acid.

7 1-[4-amino-2-(N-ethyl-N-phenylsulphamyl)phenylazol-Z-amino-S- a-chloroacryloyl chloride D naphthoLfi-sulphonic acid.

R dn fl-chloroacryloyl chloride Do.

9 do aifizfl-trichloro-acryloyl chloride Do.

10 1-[4'-aminc-2-(N-phenylsulphamyl)phenylazo]'?ramino-8-naphtholdo Do.

G-sulphonic acid.

11 1-[3:aimino-4 (phenoxy)phcnylazo]-2-am1no-8-naphthol-fi-sulphonic Acryloyl chloride Bordeaux,

aci

12 1-[3- a1mino-4-(phenoxy)phenylazo]-?rnaphthylamiue-fi sulphonic ..do Yellowish-orange,

aoi

of the monosodium salt of Z-amino-S-naphthol-(S-sulaqueous solution of The following table gives further examples of the new dyestuffs of the invention which are obtained by diazotisin-g the amines listed in thesecond column of the table and coupling the resulting diazo compounds with the coupling components listed in the third column of the table by methods similar to that described in Example 2. The fourth column of the table lists the shades obtained when the resulting dyestuffs are applied to woollen phonic acid in 100 parts of water is then added. The textile materials.

Amine Coupling Component Shade 2-anino-4: 4-bis (acryloylamino)diphenyl do. 2-arniiuo-4: 4-bis (acryloylarnino) diphenylmcthane Q-aIniino- I:4-bis(acryloylam henylethane. o

do 2-arriiinc-4:4-bis(acryloylamino)stilbene o Z-amiino-4-acryloylaminostilbene- 0.... 3-amino-5-acryl0ylamino-2 :4 6-trimethylbenz oplgenone. o

3-amino-5-acryloylaminobenzanilidc Z-arniinoA 4-bis (acryloylmnino) -5: 5-dimethyldiphenyl.

3-aIn1ino-5-acryloylaminobenz-N-ethylanilide: I I I: I I: I:

2-naphthylamine-fi-sulphonic acid 2-naphthylamine-5-sulphonic acid 2-naphthylamine-7-sulphonic acid 2-amino-8-naphthol-G-sulphonic acid 2-naphthylamine-5-sulphonic acid. 2-naphthylamine-G-sulphonic acid.

2-naphthylamine-7-sulphonic acid. 2-amino-8-naphthol-6-sulph0nio acid 2-naphthylamine-S-sulphonic acid- Z-naphthylamine-fsulphonic acid. 2-naphthylamine-7-sulphonic acid. 2-amino-8-naphth0l-6-sulphonic acid. 2-naphthy1amine-6'su1phonic acid. 2-amino-8-naphthol-fi-sulphonic acid. 2-naphthylamine-dsulphonic acid.

Z-naphthylamine-G-sulphonic acid 2-arn1ino-8-naphthol-6-sulphonic acid o 2-naghthylamine-6-sulphonic acid o 2'amino-4-acryloylaminobenzanilide. do

l d-4acry1oylaminobenzene sulphon-N-ethyll 1 2-an1ino- -acr sulphoanilide.

- .do 2-amino-4 4-l)is (acryloylamino) -5 5 -dimethoxydiphenyl.

yloylaminobenzene sulphon-N-methyl-3- 2-naphthylamine-S-sulbhonic acid. 2-naphthylamine-7-sulphonic acid. 2-argno-8-naphthol-6-sulphonic acid.

- o 2-naphthylamine-5-sulphonic acid. 2-naphthylamine-fi-sulphonic acid- 2-naphthylamine-7-sulphonic acid.

2-angina-8-naphthol-6-sulphonic acid.--.

- o Z-Baphthylamine-5-sulphonic acid. 2-naphthylamine-6-sulphonic acid. 2-naghthylaminefl-sulphonic acid. o

2-11aphthylamine-5-sulphonic acid. 2-naphthylamine-S-sulphonic acid 2-Maine-8maphthol-G-sulphonic ac o Z-naphthylamine-fi-sulphonic acid 2-naphthylamine-dsulphonic acid. 2-naghthylamineJ-sulphonic acid o 2-naphthylamine-5-sulphonic acid 2-naphthylamine-6-sulphonic acid 2-a1n1ino-8maphthol-G-sulphonic am 2-naphthylamine-G-sulphonic acid Yellowish-orange.

Do. Yellowish-red. Yelllgwish-orange.

Do. Yellowish-red. Yellowish-orange.

Do. Bluish-red. Reddish-orange. Blulsh-red. Yellcwish-orange.

D o. Yellowish-red.

Orange. Yellowish-red.

o. Yellowish-orange.

Do. Yellowish-red.

Do. Yellowish-orange.

Do. Yellowish-red.

Do. Yellowish-orange.

Do. Do.

Do. Do.

Yellowish-red.

Yellowish-orange.

Do. Do.

Do. Yellowish-red. Red.

Orange.

Example 6 2 A solution of 7.5 parts of the monosodium salt of '1 [4 amino 2' (N methyl N {3" sulphophenyl}sulphamyl)phenylazo]-2-na.phth0l in a mixture of 300 parts of water and 300 parts of acetone is cooled to 5 C. and 12 parts of acryloyl chloride are then added during minutes, the pH of the mixture being maintained at 7 by the simultaneous addition of an aqueous solution of sodium carbonate. The resulting mixture is stirred for 3 hours at a temperature between5 and 10 C., 80 parts of sodium chloride are added and the precipitated dyestuif is filtered off, washed with a 5% aqueous solution of sodium chloride and dried.

When applied to woollen textile materials from a neutral or slightly acid dyebath the dyestuii yields bluish-red shades which possess excellent fastness to light and to wet treatments.

The monosodium salt of the azo compound used in the above example may itself be obtained by diazotising 5 nitro 2 aminobenzenesulphon N methylanilide- 3'-sulphonic acid, coupling the resulting diazo compound with {i-naphthol in aqueous alkaline medium and finally treating the resulting compound with a hot aqueous solution of sodium sulphide to reduce the nitro group to an amino group.

The following table gives further examples of new dyestuffs of the invention which are obtained by replacing the 7.5 parts of the monosodiumsalt of the aminoazo compound used in Example 62 with equivalent amounts of the sodium salts of the aminoazo compounds which are obtained by coupling diazotised 5-nitro-2-aminobenzene sulphon-N-methylanilide-3-sulphonic acid with the coupling components listed in the second column of the table and subsequently reducing the nitro group to an amino group. The third column of the table gives the shades obtained when the resulting dyestuffs are applied to woollen textile materials.

Example Coupling Component Shade 1-(4-rnethylpl1enyl)-3-methyl-5-pyrazolone-- Yellow. 1-phenyl-3-methyl-5-pyrazolone Do. Acetoacetanilide..... Greenishyellow. Acet0acct-2:4-dimethylanilide Do. 67.-.. 4-methylphenol Yellow.

Example 68 5 parts of a 2 N aqueous solution of sodium nitrite are added, with stirring, to a mixture of 4.5 parts of the monosodium salt of 2-amino-4-acryloylaminobenzene sulphon-N-ethyl-3-sulphoanilide, 100 parts of water, 20 parts of ice and 5 parts of a concentrated aqueous solution of hydrochloric acid, and the resulting mixture is stirred for 15 minutes at 0 to 5 C. Sulphamic acid is then added to destroy any nitrous acid still present, folum hydroxide in parts of water, and the mixture is stirred for 4 hours at 0 to 5 C. The pH of the mixture is then adjusted to 7, 25 parts of sodium chloride are added, and the precipitated dyestuif is filtered off, washed with a 10% aqueous solution of sodium chloride, and

dried.

When applied to woollen textile materials from a neutral or weakly acid dyebath the dyestufl yields yellow' treatments. I

' The following table gives further examples of new dye- 12 destroyed by the addition of sulphamic acid, and the mixture is then neutralised to Congo red by the addition of sodium acetate. The resulting mixture is added to a solution of 2.4 parts of the sodium salt of Z-acryloyl} amino-8-naphthol-6-sulphonic acid in 100 parts of water amino)-5:5'-dimethyldiphenyl in 20 parts of acetic acid is added to a mixture of 6 parts of concentrated aqueous hydrochloric acid, 20 parts of ice and 150 parts of water. 4 parts of a 2N aqueous solution of sodium nitrite are then added and the resulting mixture is stirred. at to C. for /2 hour. Excess nitrous acid is then destroyed by the addition of sulphamic acid and the mixture is neut ralised to Congo red by the addition of sodium acetate. The resulting mixture isthen added to a solution of 1.85 parts of the sodium salt of 1'-(4-methyl-2-sulphophenyl)- 3-methyl-5-pyrazolone in 200 parts of'water at 0 to 5 C., and the pH of the mixture is adjusted to 8 by the addition of an aqueous solution of sodium hydroxide, 160 parts of acetone are then added, and the mixturev is stirred at 0 to 5 C. for 4 hours. The pH of the mixture is then adjusted to 7, 80 parts of sodium chloride are added, and the precipitated dyestuif is filtered off, washed with a 10% aqueous solution of sodium chloride and dried. When applied to wool from a neutral or weakly acid dyebath the dyestuflf yields reddish-yellow shades possessing excellent fastness to light and to wet treatments.

Example 77 and the mixture stirred for 4 hours at 0 to 5 7 ing mixture being 5 stuffs of the invention which are obtained when the 1.74 at 0 to 5 C. The pH of the mixture is adjusted to 7 parts of 1-phenyl-3-methyl-5-pyrazolone used in Example and the mixture then stirred at 0 to 5 C. for 16 hours. 68 are replaced by equivalent amounts of the coupling The resulting dyestutf is then filteredotf. The dyestuif components listed 1n the second column of the table. The is dissolved in a mixture of 1000 parts of water and 160 third column of thetable lists the shades obtalned when 10 parts of acetone, the solution is filtered and the resulting the resulting dyestuffs are applied to woollen textile matefiltrate is treated with 100 parts of sodium chloride. The rials. precipitated dyestulf is then filtered oil and dried. When 7 I applied to wool from a neutral or Weakly acid dyebath Example Coupling Component Shade the dyestuff yields yellowish-red shades possessing excel- V 15 lent fastness to wet treatments and to light. 69 Acetlmet'4'(acryhylammmanmde g ggg The following table gives further examples of the dye- 70 1-(4-acry1l0ylam1nophenyl)-3-rnethyl-5- Yellow. stuffs of the invention which are obtained when the amines pyrazo one. 1 pheny1 3 carmmwymome listed 1n the second columnof the table are diazotised I-phenyl-B-methyl-5-aminopyrazole Do. and coupled with the couphng components listed mthe l-gir-lseulphamylphenyl)-3methyl-5-py 20 third column of the table by methods similar to those de- Acetocet-o-anlsidide Gretitlishscribed inExamples 76 and 77. The fourth column of A t t m 'iud the table lists the shades obtained when the resulting dyestuifsare applied to woollen textile materials.

Example Amine Coupling Component Shade 78 4-amlno-2:4-bis(acryloylamino)-diphenylamine 2-acryloylamino-8-naphthol-6-sulphonic acid Ycllowish red. 79- 2-amtno-4:4-bls(acryloylamlno)-5z5-dimethyldiphenyl 2-acryloyla-min0-5-naphth0l-7-sulph0n1c acid Red. 80, 2-amino-4:4-bis(acryloylamino)-diphenyl 1-(4:8-disulphonaphth-2-yl)3-methyl-5-pyrazolon Reddish-yellow. 81 do Acetoacetanilidet-sulphonic'acid. Yellow.

d 1-(2-chloro-6-methyl-4-sulphophenyl)-3-methyl-5- Reddish-yellow.

pyrazolone.

. 1-acryloylamino-8-naphthol-3 :(idisulphonic acid Bluish-red.

2-acryloylamino-fi-naphthol-7-sulphonic acid Scarlet. 2-naphthol-6-sulph0nic acid; Yellowish-red. 2-na hthol-6.8-disulphom'c aci o 1-naphth0l-4-sulphonic acid- Do.

l-naphthol-B:Sfl-trisulphonic acid Reddish-orange. l-(4-acryloylamino-3-sul hophenyl)-3-carboxy-5- Golden orange. pyrazolone. 2-amino-4:4-his(acryloylamlno)-5:5-dimethyldiphenyl 1-(3-acryloylani1ino-4-sulphophenyl)-3-methyl-5- Greenish-yellow. w ammopyrazo e. 91 do l-amino-Z-(4-nitropheny1az0)-8-naphthol-3:G-disul- Greenish-blue.

phonic acid. s K I Example 76 Example 92 V v A sohmon of Parts of bls acry1oyl 45 A solution of 5.8 parts of 5-nitro-2-aminobenzene sulphon(4-acetylamino)anilide in 100 parts of hot acetic acid is poured into a mixture of 50 parts of ice, 11 parts of a concentrated aqueous solution of hydrochloric acid and 200 parts of water, and 20 parts of a N aqueous solution of sodium nitrite are then added. The resulting mixture is stirred for 30 minutes at 0 to 5 C., and sulphamic acid is then added to destroy any nitrous acid still present. A solution of 5.6 parts of the sodium salt of Z-amino-8-naphthol-6-sulphonic acid in 200 parts of water is then added, the pH of the mixture adjusted to 4, C. A concentrated aqueous solution of ammonia is added until the pH of the mixture is 8, the mixture is heated to 90 C., and'a solution of 8.2 parts of crystalline sodium sulphide in 30 parts of water added. The mixture is then stirred for 1 hour, cooled to 60 C., and the precipitated solid filtered 0E and washed with a 5% aqueous solution of sodium chloride. The solid is then dissolved in a solution of 12 parts of sodium hydroxide in 250 parts of water, and the solution heated for 3 hours at to C. The solution is then cooled to 20 C., acidified with acetic acid, and the precipitated solid is filtered off. The solid is dissolved in a mixture of 280 parts of water and 200 parts of acetone and 22 parts of acryloyl chloride are then added during 1 hour, the temperature of the resultmaintained between 0 and 5 C., and the pH of the mixture being maintained at 6 to 7 by the addition of a 10% aqueous solution of sodium carbonate. The mixture is then stirred for 3 hours at 2 C., 40 parts of sodium chloride are added and, after removal of the acetone, the precipitated dyestutf is filtered off and dried.

Example 93 In place of the 5.6 parts of the sodium salt of Z-amino- 8-naphthol-6-sulphonic acid used in the above example there are used 6.9 parts of the sodium salt of l-anilinonaphthalene-S-sulphonic acid whereby a dyestuff is obt-ained which dyes wool in bluish-red shades possessing excellent fastness to light and to wet treatments.

Example 94 In place of the 22 parts of acryloyl chloride used in Examples 92 or 93 there are used 30 parts of a-chloroacryloyl chloride when similar dyestuffs are obtained.

2-amin0-4 4-bis(acryloylamino 5-dimethyldiphenyl,

2-amino-4 4-b.is(-acryloylamino -5 5 -dimeth-oxydiphenyl,

2-amino-4 4-bis acryloylamino) diphenylmethane,

2-amino-4,4-bis- (acryloylamino stilbene,

4-a-mino-2:4'-bis(acryloylamino)-diphenylamine,

2-amino-4-acryloylaminostilbene,

3-amino-5-acryloylaminobenzanilide,

3 -amino-5aacryloylaminobenz-N-ethylanilide,

2-amino-4-acryloylaminobenzanilide,

Z-amino-4acryloylaminobenz-N-ethylanilide,

2-amino-4 4-bis(acryloylamino -benzanilide,

3 -amino-5-acryloylamino-2' :4 6-trimethylbenzophenone,

2-amino-4-acryloylaminobenZenesulphon-N-ethylanilide,

2-amino-4-acryloylaminobenzenesulphon-N-ethyl-3 sulphoanilide and 2-amino-4-acryloylaminob enzenesulphon-N-methyl-3 sulphoanilide 7 used in .the above examples may be obtained by methods similar to that described in Example 1 for 2-am.ino-4:4- bis(acryloylamino)diphenyl starting from the appropriate nitroamine or nitrodiamino compounds.

1 4 What we claim is: The azo dyestuffs of the formula wherein Y Y and Y are independently selected from the class consisting of hydrogen and chlorine atoms; V represents a radical selected from the class consisting of lower alkyl and lower alkoxy radicals; n represents a positive integer not exceeding 2; X is selected from the class consisting of a direct link and -CII CH2, CH=CH, -0H o, co-, -CON s0 N- and -N- It I'l and wherein R is selected from the class consisting of hydrogen and lower alkyl; A represents a .phenylene radical and any substituents on said phenylene radical are selected from the class consisting of methyl, methoxy, chlorine, bromine and sulphonic acid; Z is selected from the class consisting f hydrogen and Y2 .CO.C=C/

it Y E represents the residue of a coupling component selected from the class consisting of residues of coupling components of the phenol, naphthol, acetoacetanilide, naphthylamine, S-aminopyrazole and 5-pyrazolone coupling components; at least one of A and E containing at least one group selected from the class consisting of sulphonic acid and carboxylic acid groups.

References Cited by the Examiner UNITED STATES PATENTS 3,098,063 7/63 Eisele et al 260-163 FOREIGN PATENTS 211,447 10/60 Austria. 858,183 1/61 Great Britain.

CHARLES B. PARKER, Primary Examiner. 

